Derivatives of (1-benzyl-piperidine-4-yl)-diphenyl-methanol and their use as pesticide

ABSTRACT

Compounds of formula (I), wherein R 1  and R 2  are, for example, hydrogen, halogen, C 1 -C 6 -alkyl, C 3 -C 6 cycloalkyl, halo-C 1 -C 6 alkyl, C 1 -C 6 alkoxy or halo-C 1 -C 6 alkoxy; R 3  and R 4  are hydrogen or together form a bond; R 5  is, for example, C 1 -C 6 alkyl C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl or C 2 -C 4 alkenyl; R 55  is, for example, hydrogen, C 1 -C 6 alkyl or halo-C 1 -C 6 alkyl; R 6  is, for example, hydrogen, halogen, CN, NO 2  C 1 -C 6 alkyl, halo-C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, halo-C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkoxy, C 1 -C 6 alkoxy, halo-C 1 -C 6 alkoxy, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl or halo-C 2 -C 4 alkenyl; m is 1, 2, 3, 4 or 5; n is 1, 2, 3, 4, or 5; o is 1, 2, or 3: q is 0 or 1; s is 1, 2, 3, 4 or 5; and, where applicable, E/Z isomers, mixtures of E/Z isomers and/or tautomers, in each case in free form or in salt form; a process for the preparation of and the use of those compounds, pesticidal compositions in which the active ingredient has been selected from those compounds or an agrochemically acceptable salt thereof, a process for the preparation of and the use of those compositions, plant propagation material that has been treated with those compositions, and a method of controlling pests are described.

The present invention relates to (1) a compound of formula

-   -   wherein    -   R₁ and R₂ are each independently of the other hydrogen, halogen,        C₁-C₆alkyl, C₃-C₆-cycloalkyl, halo-C₁-C₆alkyl,        halo-C₃-C₆cycloalkyl, C₂-C₄alkenyl, C₂-C₄alkynyl,        halo-C₂-C₄alkenyl, halo-C₂-C₄alkynyl, C₁-C₆alkoxy,        halo-C₁-C₆alkoxy, C₂-C₆alkenyloxy, C₂-C₆alkynyloxy,        halo-C₂-C₆alkenyloxy, halo-C₂-C₆alkynyloxy, —SF₅, —C(═O)N(R₇)₂,        —O—C(═O)N(R₇)₂, —CN, —NO₂, —S(═O)₂N(R₇)₂, —S(═O)_(p)—C₁-C₆alkyl,        —S(═O)_(p)-halo-C₁-C₆alkyl, —O—S(═O)_(p)—C₁-C₆alkyl,        —O—S(═O)_(p)-halo-C₁-C₆alkyl, phenyl, benzyl, phenoxy or        benzyloxy, wherein each of the phenyl, benzyl, phenoxy or        benzyloxy radicals is unsubstituted or is substituted in the        aromatic ring by from one to five substituents selected        independently of one another from the group consisting of        halogen, cyano, NO₂, C₁-C₆alkyl, halo-C₁-C₆alkyl, C₁-C₆alkoxy        and halo-C₁-C₆alkoxy;    -   R₃ and R₄ are hydrogen or together form a bond;    -   R₅ is C₁-C₆alkyl, halo-C₁-C₆alkyl, C₃-C₆cycloalkyl,        C₂-C₄alkenyl, C₂-C₄alkynyl, C₁-C₆-alkoxy, C₁-C₆alkoxyalkyl,        halo-C₁-C₆alkoxy, C₂-C₆alkenyloxy, C₂-C₆alkynyloxy,        C₁-C₆alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, halogen        or hydroxy;    -   R₅₅ is hydrogen, C₁-C₆alkyl, halo-C₁-C₆alkyl, C₃-C₆cycloalkyl,        C₂-C₄alkenyl, C₂-C₄-alkynyl, C₁-C₆alkoxy, C₁-C₆alkoxyalkyl,        halo-C₁-C₆alkoxy, C₂-C₆alkenyloxy or C₂-C₆alkynyloxy;    -   R₆ is hydrogen, halogen, CN, NO₂, C₁-C₆alkyl, halo-C₁-C₆alkyl,        C₃-C₆cycloalkyl, halo-C₃-C₆cycloalkyl, C₃-C₆cycloalkoxy,        C₁-C₆alkoxy, halo-C₁-C₆alkoxy, C₂-C₄alkenyl, C₂-C₄-alkynyl,        halo-C₂-C₄alkenyl, halo-C₂-C₄alkynyl, C₂-C₆alkenyloxy,        C₂-C₆alkynyloxy, halo-C₂-C₆-alkenyloxy, halo-C₂-C₆alkynyloxy,        —C(═O)-C₁-C₆alkyl, —C(═O)-halo-C₁-C₆alkyl, —C(═O)—OC₁-C₆alkyl,        —C(═O)—O-halo-C₁-C₆alkyl, —N(R₇)₂, —C(═O)N(R₇)₂, —O—C(═O)N(R₇)₂,        —S(═O)₂N(R₇)₂, —S(═O)_(p)—C₁-C₆alkyl,        —S(═O)_(p)-halo-C₁-C₆alkyl, —O—S(═O)_(p)—C₁-C₆alkyl,        —O—S(═O)_(p)-halo-C₁-C₆alkyl, —NR₁₂—C(═Y)-Z-R₁₃, —C(R₉)═N—W—R₁₀,    -   benzyl, phenoxy, benzyloxy; or phenyl, benzyl, phenoxy,        benzyloxy, heterocyclyl or heterocyclyloxy each of which is        substituted by from one to five substituents selected        independently of one another from the group consisting of        halogen, cyano, NO₂, C₁-C₆alkyl, C₃-C₈cycloalkyl,        C₃-C₈cycloalkyl-C₁-C₆alkyl, halo-C₁-C₆alkyl, C₁-C₆alkoxy,        C₃-C₈cycloalkoxy, C₃-C₈cycloalkoxy-C₁-C₆alkyl,        C₃-C₈cycloalkyl-C₁-C₆alkoxy, halo-C₁-C₆alkoxy, C₂-C₄alkenyl,        C₂-C₄alkynyl, halo-C₂-C₄alkenyl, halo-C₂-C₄alkynyl,        C₂-C₆alkenyloxy, C₂-C₆alkynyloxy, halo-C₂-C₆alkenyloxy,        halo-C₂-C₆alkynyloxy, —N(R₈)₂, phenyl, benzyl, phenoxy,        benzyloxy, heterocyclyl and heterocyclyloxy;    -   the two R₇ radicals are each independently of the other        hydrogen, C₁-C₁₋₂alkyl, halo-C₁-C₁₂alkyl, C₂-C₁₂alkenyl,        halo-C₂-C₁₂alkenyl, C₂-C₁₂alkynyl, halo-C₂-C₁₂alkynyl,        —C(═O)—R₁₀, —C(═S)—R₁₀, —C(═O)—O—R₁₀, —C(═S)—O—R₁₀,        —C(═O)—NR₁₀R₁₁, —C(═S)—NR₁₀R₁₁, —S(═O)_(p)—R₁₀, C₃-C₈cycloalkyl,        aryl, aryl-C₁-C₆alkyl, heterocyclyl, heterocyclyl-C₁-C₆alkyl; or        C₃-C₉cycloalkyl, aryl, aryl-C₁-C₆alkyl, heterocyclyl or        heterocyclyl-C₁-C₆alkyl which, depending upon the possibilities        of substitution, are each substituted in the ring by from one to        five substituents selected independently of one another from        halogen, hydroxy, cyano, nitro, C₁-C₆alkyl, halo-C₁-C₆alkyl,        C₁-C₆alkoxy and halo-C₁-C₆alkoxy; or    -   together, with the nitrogen atom to which they are bonded, form        a heterocyclic ring that is unsubstituted or substituted;    -   R₈ is hydrogen, C₀-C₆alkyl or benzyl;    -   R₉ is halogen, C₁-C₆alkyl, C₃-C₈cycloalkyl,        C₃-C₈cycloalkyl-C₁-C₆alkyl, halo-C₁-C₆alkyl, C₁-C₆alkoxy,        C₃-C₈cycloalkoxy, C₃-C₈cycloalkoxy-C₁-C₆alkyl, halo-C₁-C₆alkoxy,        —NH(C₁-C₆-alkyl) or —N(C₁-C₆alkyl)₂;    -   R₁₀ and R₁₁ are each independently of the other hydrogen,        C₁-C₆alkyl, C₃-C₈cycloalkyl, C₃-C₈cycloalkyl-C₁-C₆alkyl,        halo-C₁-C₆alkyl, C₂-C₄alkenyl, C₂-C₄alkynyl, halo-C₂-C₄alkenyl,        halo-C₂-C₄alkynyl or —C(═O)-C₁-C₆alkyl;    -   R₁₂ is hydrogen, C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl,        C₃-C₈cycloalkyl, halo-C₁-C₆alkyl, C₂-C₆alkenyl or C₂-C₆alkynyl;    -   R₁₃ is hydrogen, C₁-C₆alkyl, halo-C₁-C₆alkyl,        C₁-C₆alkoxy-C₁-C₆alkyl, C₃-C₈cycloalkyl, halo-C₁-C₆alkyl,        halo-C₃-C₈cycloalkyl, C₂-C₆alkenyl, C₂-C₆alkynyl,        halo-C₂-C₆alkenyl, halo-C₂-C₆alkynyl, aryl, aryl-C₁-C₆alkyl or        heterocyclyl, or aryl, aryl-C₁-C₆alkyl or heterocyclyl each of        which is substituted by from one to three substituents selected        from the group consisting of halogen, cyano, NO₂, C₁-C₆alkyl,        C₃-C₈cycloalkyl, halo-C₁-C₆alkyl, C₁-C₆alkoxy, halo-C₁-C₆alkoxy,        C₂-C₄alkenyl, C₂-C₄alkynyl, halo-C₂-C₄alkenyl,        halo-C₂-C₄alkynyl, C₂-C₆alkenyloxy and C₂-C₆alkynyloxy;    -   m is 1, 2, 3, 4 or 5;    -   n is 1, 2, 3, 4 or 5;    -   o is 1, 2 or 3;    -   p is 0, 1 or 2;    -   q is 0 or 1;    -   s is 1, 2, 3, 4 or 5;    -   Y is O or S;    -   Z is a bond, O, S or NR₁₄;    -   R₁₄ is hydrogen, C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl,        C₃-C₈cycloalkyl, halo-C₁-C₆alkyl, C₂-C₆alkenyl or C₂-C₆alkynyl;    -   W is O or NH or N-C₁-C₆alkyl;    -   and, where applicable, to E/Z isomers, mixtures of E/Z isomers        and/or tautomers, in each case in free form or in salt form;    -   to a process for the preparation of and to the use of those        compounds, to pesticidal compositions in which the active        ingredient has been selected from those compounds or an        agrochemically acceptable salt thereof, to a process for the        preparation of and to the use of those compositions, to plant        propagation material that has been treated with those        compositions, and to a method of controlling pests.

Certain piperidine derivatives are proposed in the literature as activeingredients in pesticides. The biological properties of those knowncompounds are not, however, entirely satisfactory in the area of pestcontrol, for which reason there is a need to provide further compoundshaving pesticidal properties, especially for the control of insects andmembers of the order Acarina, that problem being solved according to theinvention by the provision of the present compounds of formula (I).

The compounds of formula (I) and, where applicable, their tautomers canform salts, for example acid addition salts. These acid addition saltsare formed, for example, with strong inorganic acids, such as mineralacids, for example sulfuric acid, a phosphoric acid or a hydrohalicacid, with strong organic carboxylic acids, such as unsubstituted orsubstituted, for example halo-substituted, C₁-C₄alkanecarboxylic acids,for example acetic acid, unsaturated or saturated dicarboxylic acids,for example oxalic acid, malonic acid, maleic acid, fumaric acid orphthalic acid, hydroxycarboxylic acids, for example ascorbic acid,lactic acid, malic acid, tartaric acid or citric acid, or benzoic acid,or with organic sulfonic acids, such as unsubstituted or substituted,for example halo-substituted, C₁-C₄alkane- or aryl-sulfonic acids, forexample methane- or p-toluene-sulfonic acid. Compounds of formula (I)that have at least one acidic group can furthermore form salts withbases. Suitable salts with bases are, for example, metal salts, such asalkali metal salts or alkaline earth metal salts, for example sodium,potassium or magnesium salts, or salts with ammonia or with an organicamine, such as morpholine, piperidine, pyrrolidine, a mono-, di- ortri-lower alkylamine, for example ethylamine, diethylamine,triethylamine or dimethylpropylamine, or a mono-, di- ortri-hydroxy-lower alkylamine, for example mono-, di- ortri-ethanolamine. Corresponding internal salts may also be formed whereappropriate. The free form is preferred. Among the salts of thecompounds of formula (I), the agrochemically advantageous salts arepreferred. Hereinbefore and hereinafter, any reference to the freecompounds of formula (I) or their salts is to be understood asincluding, where appropriate, also the corresponding salts or the freecompounds of formula (I), respectively. The same applies to tautomers ofcompounds of formula (I) and salts thereof.

Unless defined otherwise, the general terms used hereinbefore andhereinafter have the meanings given below.

Halogen—as a group per se and as a structural element of other groupsand compounds, such as haloalkyl, halocycloalkyl, haloalkenyl,haloalkynyl and haloalkoxy—is fluorine, chlorine, bromine or iodine,especially fluorine, chlorine or bromine, more especially fluorine orchlorine, especially chlorine.

Unless defined otherwise, carbon-containing groups and compounds eachcontain from 1 up to and including 20, preferably from 1 up to andincluding 18, more especially from 1 up to and including 10, especiallyfrom 1 up to and including 6, more especially from 1 up to and including4, especially from 1 up to and including 3, especially 1 or 2, carbonatoms, methyl being most especially preferred.

Alkyl—as a group per se and as a structural element of other groups andcompounds, such as, for example, haloalkyl, alkoxy, alkoxyalkyl,haloalkoxy, alkoxycarbonyl, alkylthio, haloalkylthio, alkylsulfonyl andalkylsulfonyloxy—is, in each case giving due consideration to the numberof carbon atoms contained in the group or compound in question, eitherstraight-chained, e.g. methyl, ethyl, n-propyl, n-butyl, n-hexyl,n-octyl, n-decyl, n-dodecyl, n-hexadecyl or n-octadecyl, or branched,e.g. isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl orisohexyl.

Alkenyl and alkynyl—as groups per se and as structural elements of othergroups and compounds, such as haloalkenyl, haloalkynyl, alkenyloxy,haloalkenyloxy, alkynyloxy or haloalkynyloxy—are straight-chained orbranched and each contains two or preferably one unsaturatedcarbon-carbon bond(s). Examples are vinyl, prop-2-en-1-yl,2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, prop-2-yn-1-yl,but-2-yn-1-yl and but-3-yn-1-yl.

Cycloalkyl—as a group per se and as a structural element of other groupsand compounds, such as, for example, alkyl—is cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. Cyclopentyl andcyclohexyl, and especially cyclopropyl, are preferred.

Halo-substituted carbon-containing groups and compounds, such ashaloalkyl and haloalkoxy, may be partially halogenated orperhalogenated, it being possible in the case of polyhalogenation forthe halogen substituents to be the same or different. Examples ofhaloalkyl—as a group per se and as a structural element of other groupsand compounds, such as haloalkoxy—are methyl substituted from one tothree times by fluorine, chlorine and/or bromine, such as CHF₂, CF₃ orCH₂Cl; ethyl substituted from one to five times by fluorine, chlorineand/or bromine, such as CH₂CF₃, CF₂CF₃, CF₂CCl₃, CF₂CHCl₂, CF₂CHF₂,CF₂CFCl₂, CH₂CH₂C₁, CF₂CHBr₂, CF₂CHClF, CF₂CHBrF or CClFCHClF; propyl orisopropyl substituted from one to seven times by fluorine, chlorineand/or bromine, such as CH₂CHBrCH₂Br, CF₂CHFCF₃, CH₂CF₂CF₃, CF₂CF₂CF₃,CH(CF₃)₂ or CH₂CH₂CH₂Cl; and butyl or an isomer thereof substituted fromone to nine times by fluorine, chorine and/or bromine, such asCF(CF₃)CHFCF₃, CF₂(CF₂)₂CF₃ or CH₂(CF₂)₂CF₃.

Aryl is especially phenyl or naphthyl, preferably phenyl.

Heterocyclyl is a 5- to 7-membered saturated or unsaturated ring whichis preferably aromatic and which has from one to four hetero atomsselected from the group consisting of N, O and S. Preference is given toaromatic 5- and 6-membered rings that have a nitrogen atom as heteroatom and that may have a further hetero atom, preferably nitrogen orsulfur, especially nitrogen. Preferred heterocyclyl radicals are, forexample, pyrrolyl, pyrazolyl, imidazolyl, 1,2,4-triazolyl,1,2,4-oxadiazolyl, tetrazolyl, pyrazinyl, pyridyl, pyrimidinyl,pyridazinyl, thiazolyl, isothiazolyl, isoxazolyl, indolyl, indazolyl,benzimidazolyl, benzothiazolyl, furanyl, tetrahydrofuranyl and thienyl;preference is given to tetrazolyl, especially tetrazolyl that issubstituted by C₁-C₃alkyl, especially methyl, ethyl, propyl orisopropyl, more especially by ethyl.

Preferred embodiments within the scope of the invention are

-   -   a compound according to the above group (1) of formula (I)        wherein    -   R₁ and R₂ are each independently of the other halogen,        C₁-C₂alkyl, C₃-C₆cycloalkyl, halo-C₁-C₂alkyl, C₁-C₂alkoxy,        halo-C₁-C₂alkoxy, —C(═O)N(CH₃)₂, —CN or —NO₂;    -   especially are each independently of the other halogen,        C₁-C₂alkyl, halo-C₁-C₂alkyl, C₁-C₂alkoxy or halo-C₁-C₂alkoxy;    -   more especially are each independently of the other chlorine,        bromine, methyl, tri-fluoromethyl, methoxy or trifluoromethoxy;    -   even more especially are each independently of the other        chlorine, trifluoromethyl or trifluoromethoxy;    -   most especially wherein the two substituents are CF₃, are in        para-position and m and n are 1;    -   (3) a compound according to (1) or (2) of formula (I) wherein R₃        and R₄ are hydrogen;    -   especially wherein R₃ and R₅ are cis to each other;    -   (4) a compound according to (1) or (2) of formula (I) wherein R₃        and R₄ together form a bond;    -   a compound according to any one of groups (1) to (4) of        formula (I) wherein    -   R₅ is C₁-C₆alkyl or halo-C₁-C₆alkyl; especially methyl or ethyl;        more especially methyl;    -   a compound according to any one of groups (1) to (3) and (5) of        formula (I) wherein o is 1 and R₅ is in the 3-position on the        piperidine ring; especially wherein R₃ and R4 are hydrogen and        R₃ and R₅ are in the cis-configuration;    -   (7) a compound according to any one of groups (1) to (6) of        formula (I) wherein    -   R₆ is —NR₁₂—C(═Y)—Z—R₁₃ and R₁₃ is C₁-C₆alkyl,        C₁-C₆alkoxy-C₁-C₆alkyl, C₃-C₈cycloalkyl, halo-C₁-C₆alkyl,        halo-C₃-C₈cycloalkyl, C₂-C₆alkenyl, C₂-C₆alkynyl,        halo-C₂-C₆alkenyl or halo-C₂-C₆alkynyl;    -   (8) a compound according to any one of groups (1) to (6) of        formula (I) wherein    -   R₆ is —N(R₇)₂ and the two R₇ radicals are each independently of        the other hydrogen, C₁-C₁₂alkyl, halo-C₁-C₁₂alkyl,        C₂-C₁₂alkenyl, —C(═O)—R₁₀, —C(═S)—R₁₀, —C(═O)—O—R₁₀,        —C(═S)—O—R₁₀, —C(═O)—NR₁₀R₁₁, —C(═S)—NR₁₀R₁₁ or —S(═O)_(p)—R₁₀,    -   especially wherein R₆ is —NHR₇ and R₇ is —C(═O)—O—R₁₀;    -   (9) a compound according to (8) of formula (I) wherein    -   R₁₀ and R₁₁ are each independently of the other hydrogen,        C₁-C₆alkyl, C₃-C₈cycloalkyl, C₃-C₈cycloalkyl-C₁-C₆alkyl,        halo-C₁-C₆alkyl, C₂-C₄alkenyl, C₂-C₄alkynyl, halo-C₂-C₄alkenyl,        halo-C₂-C₄alkynyl or —C(═O)-C₁-C₆alkyl;    -   especially hydrogen, C₁-C₂alkyl, C₃-C₈cycloalkyl,        C₁-C₂halogenalkyl or —C(═O)-C₁-C₆-alkyl;    -   (12) a compound according to (8) of formula (I) wherein    -   p is 1 or 2; especially 2;    -   (13) a compound according to (1) to (12) of formula (I) wherein    -   R₅₆ is hydrogen;    -   (14) a compound according to (1) to (13) of formula (I) wherein    -   q is 1;    -   (15) a compound according to (8) of formula (I) wherein    -   R₉ is halogen, C₁-C₆alkyl, C₃-C₈cycloalkyl,        C₃-C₈cycloalkyl-C₁-C₆alkyl, halo-C₁-C₆alkyl, C₁-C₆alkoxy,        C₃-C₈cycloalkoxy, C₃-C₈cycloalkoxy-C₁-C₆alkyl, halo-C₁-C₆alkoxy,        —NH(C₁-C₆-alkyl) or —N(C₁-C₆alkyl)₂;    -   (16) a compound according to (7) of formula (I) wherein    -   W is O or NH; especially O;    -   (17) a compound according to (1) to (6) and of formula (I)        wherein    -   R₆ is heterocyclyl that is unsubstituted or substituted by from        one to three substituents selected independently of one another        from the group consisting of halogen, cyano, NO₂, C₁-C₆alkyl,        C₃-C₈cycloalkyl, C₃-C₈cycloalkyl-C₁-C₆alkyl, halo-C₁-C₆alkyl,        C₁-C₆alkoxy, C₃-C₈-cycloalkoxy, C₃-C₈cycloalkoxy-C₁-C₆alkyl,        C₃-C₈cycloalkyl-C₁-C₆alkoxy, halo-C₁-C₆alkoxy, C₂-C₄alkenyl,        C₂-C₄alkynyl, halo-C₂-C₄alkenyl, halo-C₂-C₄alkynyl,        C₂-C₆alkenyloxy, C₂-C₆-alkynyloxy, halo-C₂-C₆alkenyloxy,        halo-C₂-C₆alkynyloxy and —N(R₈)₂, especially wherein R₆ is        tetrazolyl that is unsubstituted or mono-substituted by        C₁-C₆-alkyl.

Special preference is given within the scope of the invention to thecompounds of formula (I) listed in the Tables.

The invention further relates to a process for the preparation of acompound of formula (I) wherein (R₁)_(m), (R₂)_(n), R₅, R₅, R₆, O, q ands are as defined for formula (I) and R₃ and R₄ together form a bond,which comprises

-   -   (a) reacting a compound of formula    -   which is known or can be prepared by methods known per se and        wherein R is C₁-C₈alkyl and R₅, R₅₅ and o are as defined for        formula (I), with a compound of formula    -   which is known per se and wherein (R₆)_(s) is as defined for        formula (I) and X is a leaving group, to form a compound of        formula    -   wherein R, R₅, R₅₅, R₆, s and o are as defined for formulae (II)        and (III) and X is the anion of the said leaving group;    -   (b) reducing the resulting compound of formula (IV) to form a        compound of formula    -   wherein R₁, R₅, R₅₅, R₆, o, s and R are as defined for formula        (IV);    -   (c) either reacting the resulting compound of formula (V) with        two moles of a compound of formula    -   wherein (R₁)_(n) is as defined for formula (I), or    -   reacting the compound of formula (V) with one mole of a compound        of formula (VI) and then with one mole of a compound of formula    -   wherein (R₂)_(n) is as defined for formula (I),    -   to form a compound of formula    -   wherein R₁, R₅, R₅₅, R₆, m, o and s are as defined for formula        (I); and where applicable, if desired,    -   (d) reacting the resulting compound of formula (Ia) with an        oxidising agent to form a compound of formula (I) wherein q is        1.

The invention further relates to

-   -   (e) a process for the preparation of a compound of formula (I),        or a salt thereof,        wherein (R₁)_(m) and (R₂), are identical, R₅, R₅₅, R₆, o, q and        s are as defined for formula (I) and R₃ and R₄ are hydrogen,        which comprises reacting a compound of formula    -   which is known or can be prepared by methods known per se and        wherein R₅, R₅₅ and o are as defined for formula (I), in a        manner analogous to the above Process Steps (a), (c) and (d).

The invention further relates to a process for the preparation of acompound of formula (I), or a salt thereof, wherein (R₁)_(m) and(R₂)_(n) are identical, R₅, R₅₅, R₆, o, q and s are as defined forformula (I) and R₃ and R₄ are hydrogen, which comprises

-   -   (f) reacting a compound of formula (VII), in a manner analogous        to Process Step (a), with a compound of formula    -   wherein X is a leaving group;    -   (g) reacting the resulting compound of formula    -   wherein R, R₅, R₅₅, o and R are as defined for formula (VII), in        a manner analogous to Process Step (c), to form a compound of        formula    -   wherein (R₁)_(m), (R₂)_(n), R₅, R₅₅ and o are as defined for        formula (I); and, where applicable,    -   (h) for the preparation of a compound of formula (I) wherein s        is not 0, removing the benzyl group and further reacting the        resulting compound of formula    -   wherein (R₁)_(m), R₅, R₅₅ and o are as defined for formula (I),        analogously to Process Step (a) and, where applicable, (d).

(i) A process for the preparation of a compound of formula (VII), or asalt thereof, which comprises converting a compound of formula

-   -   in the presence of an acid and an alcohol of formula        HO-C₁-C₈alkyl into a compound of formula (II), or a salt        thereof;    -   (k) converting that compound of formula (II) by hydrogenation        into a compound of formula    -   and, where applicable, if desired,    -   (I) transisomerising the compound of formula (VIIa) to form a        compound of formula

The invention further relates to a process for the preparation of acompound of formula (I) as defined above and wherein R₃ and R₄ togetherform a bond, which comprises

-   -   (m) reacting a compound of formula    -   wherein R₅, R₅₅ and o are as defined for formula (1), in a        manner analogous to Process Step (c), with a compound of        formula (VI) to form a compound of formula    -   wherein (R₁)_(m), R₅, R₅₅ and o are as defined for formula (I);    -   (n) oxidising the resulting compound of formula (XII) to form a        compound of formula    -   wherein (R₁)_(m), R₅, R₅₅ and o are as defined for formula (I);    -   (o) reacting the compound of formula (XIII) in a manner        analogous to Process Steps (c) and (m) to form a compound of        formula    -   wherein (R₁)_(m), R₅, R₅₅ and o are as defined for formula (I);    -   and further reacting the resulting compound of formula (XIV) in        succession analogously to Process Steps (b), (a) and—if        desired—(d).

The invention further relates to a process for the preparation of acompound of formula (VIII) as defined above, which comprises

-   -   (p) reacting a compound of the formula    -   which is known or which can be prepared according to methods        known per se, and wherein R₅₅ and o have the same meanings as        defined under formula (I), in the presence of a base such as        K₂CO₃ and a solvent such as acetone, with a compound of the        fomula R₅—X, wherein R₅ is as defined under formula (I), and X        is a leaving group, preferably Cl or Br,    -   (q) further treating the compound thus obtained of the formula    -   wherein R₅, R₅₅ and o have the same meanings as defined under        formula (I), with an acid such as sulfuric acid,    -   (r) reacting the compound thus obtained of the formula    -   wherein R₅, R₅₅ and o have the same meanings as defined under        formula (I), preferably in the presence of a base such as        KO-tert-butyl, with TOSMIC of the formula    -   (s) treating the compound of the formula    -   thus obtained, wherein R₅, R₅₅ and o have the same meanings as        defined under formula (I), in the presence of an alcohol of the        formula HO-C₁-C₈alkyl with a acid such as sulphuric acid.

The starting materials of formulae (III), (VI), (X) and (XV) mentionedhereinbefore and hereinafter, which are used for the preparation of thecompounds of formula (I) in free form or in salt form, are known or canbe prepared by methods known per se. Some of the compounds of formulae(II), (IV), (V), (VII), (IX) to (XIV) and (XVI) to (XVIII) are novel.The invention relates to them also.

The remarks made above regarding tautomers of compounds of formula (I)apply analogously to the starting materials mentioned hereinbefore andhereinafter with regard to their tautomers.

The reactions described hereinbefore and hereinafter are carried out ina manner known per se, for example in the absence or, customarily, inthe presence of a suitable solvent or diluent or of a mixture thereof,the reactions being carried out, as required, with cooling, at roomtemperature or with heating, for example in a temperature range ofapproximately from −80° C. to the boiling temperature of the reactionmedium, preferably from approximately 0° C. to approximately +150° C.,and, if necessary, in a closed vessel, under pressure, under an inertgas atmosphere and/or under anhydrous conditions. Especiallyadvantageous reaction conditions can be found in the Examples.

The reaction time is not critical; a reaction time of from approximately0.1 to approximately 72 hours, especially from approximately 0.5 toapproximately 24 hours, is preferred.

The product is isolated by customary methods, for example by filtration,crystallisation, distillation or chromatography, or any suitablecombination of such methods.

Hereinbefore and hereinafter a leaving group is understood as being anyremovable group known to the person skilled in the art that normallycomes into consideration in chemical reactions, especially halogens,such as fluorine, chlorine, bromine, iodine, —O—C(═O)-A, —O—P(═O)(W)₂,—O—Si(C₁-C₈alkyl)₃, —O—(C₁-C₈alkyl), —O-aryl, —O—S(═O)₂W, —S—P(═O)(W)₂,—S—P(═S)(W)₂, —S—S—(C₁-C₈alkyl), —S—S-aryl, —S-(C₁-C₈alkyl), —S-aryl,—S(═O)W or —S(═O)₂W, wherein W is unsubstituted or substitutedC₁-C₈alkyl, C₂-C₈alkenyl, C₂-C₈-alkynyl, unsubstituted or substitutedaryl, unsubstituted or substituted benzyl, C₁-C₈alkoxy ordi(C₁-C₈alkyl)amine wherein the alkyl groups are independent of eachother; NO₃, NO₂, or sulfate, sulfite, phosphate, phosphite, carboxylate,imino ester, N₂ or carbamate. Especially preferred as the leaving groupare chlorine and bromine, more especially chlorine.

The starting materials mentioned hereinbefore and hereinafter that areused for the preparation of the compounds of formula (I) and, whereapplicable, their tautomers are known or can be prepared by methodsknown per se, for example as indicated below.

In the reaction according to Process Variants (a) and (f), inertsolvents are used, such as, for example, benzene, toluene, xylenes,acetonitrile, propionitrile, ethyl acetate, propyl acetate, butylacetate, acetone, diethyl ketone, methyl ethyl ketone or methyl isobutylketone. The temperature range is from room temperature to the refluxtemperature of the solvent concerned, the reflux temperature beingpreferred.

Process Variant (b): The reaction is preferably carried out in alcohols,such as, for example, methanol or ethanol, in a temperature range offrom 0° C. to +50° C., preferably at room temperature. A preferredreducing agent is sodium borohydride.

Process Variants (c), (q), (m), (o): Dialkyl ethers or tetrahydrofuranare preferably used as solvent; the reactions are carried out in atemperature range of from −70° C. to room temperature, and magnesium orn-butyllithium is used as metallating agent.

In Process Variant (d), alcohols, such as, for example, methanol orethanol, are preferably used as solvent. The procedure is preferablycarried out at room temperature. The oxidising agents used are, forexample, inorganic peroxides, such as sodium perborate, potassiumpermanganate or hydrogen peroxide; or organic peracids, such asperbenzoic acid, m-chloro-perbenzoic acid (mCPBA) or peracetic acid; ormixtures of organic acids and hydrogen peroxide, such as, for example,acetic acid/hydrogen peroxide. Especially suitable are H₂O₂ or peracids,more especially H₂O₂.

Process Variant (h): The reaction is preferably carried out in alcoholssuch as methanol or ethanol, in a temperature range of from 0 to 50° C.,especially at room temperature, under normal pressure and using acatalyst, especially palladium-on-carbon.

Process Variant (i): The hydrolysis is carried out using a mineral acid,especially hydrochloric acid or sulfuric acid, at from 20 to 150° C.,and the subsequent esterification is usually carried out with a loweralcohol, such as methanol or ethanol.

Process Variant (k): The reduction is effected with the use of acatalyst, such as, for example, PtO₂ or palladium-on-carbon, in asolvent, such as, for example, an alcohol, or in an organic acid, forexample acetic acid, with hydrogen under normal pressure or also atelevated pressure, preferably from 1 to 10 atm.

Process Variant (I): The isomerisation is effected with the use ofbases, especially alcoholates, such as, for example, sodium methanolate,in an organic solvent, such as, for example, an alcohol, for examplemethanol, and between room temperature and the boiling point of thesolvent concerned.

Process Variant (n): The process is preferably carried out in an inertsolvent such as a hydrocarbon or a halogenated hydrocarbon, such as, forexample, methylene chloride, and with dimethyl sulfoxide/oxalyl chlorideor pyridinium dichromate as oxidising agent.

Compounds of formula (I) obtainable in accordance with the process or byother methods can be converted in a manner known per se into othercompounds of formula (I) by replacing one or more of the substituents ofthe starting compound of formula (I) in a conventional manner by one (ormore) other substituent(s) according to the invention.

In so doing, depending upon the choice of reaction conditions andstarting materials suitable for the respective purpose, it is possiblefor only one substituent to be replaced by a different substituentaccording to the invention in one reaction step or for severalsubstituents to be replaced by different substituents according to theinvention in the same reaction step.

Salts of compounds of formula (I) may be prepared in a manner known perse. Salts of compounds of formula (I) with bases are obtained, forexample, by treating the free compounds with a suitable base or with asuitable ion-exchange reagent.

Salts of compounds of formula (I) may be converted in a conventionalmanner into the free compounds of formula (I), for example by treatmentwith a suitable acid or with a suitable ion-exchange reagent.

Salts of compounds of formula (I) may be converted in a manner known perse into other salts of a compound of formula (I).

The compounds of formula (I) in free form or in salt form may be in theform of one of the possible isomers or in the form of a mixture thereof,for example according to the number and the absolute and relativeconfiguration of asymmetric carbon atoms occurring in the moleculeand/or according to the configuration of non-aromatic double bondsoccurring in the molecule, they may be in the form of pure isomers, suchas antipodes and/or diastereoisomers, or in the form of mixtures ofisomers, such as mixtures of enantiomers, for example racemates,mixtures of diastereoisomers or mixtures of racemates. The inventionrelates both to the pure isomers and to all possible mixtures of isomersand is to be interpreted accordingly hereinbefore and hereinafter, evenif stereochemical details are not mentioned specifically in every case.

Mixtures of diastereoisomers, mixtures of racemates and mixtures ofdouble-bond isomers of compounds of formula (I), in free form or in saltform, that are obtainable in accordance with the process depending uponthe starting materials and procedures chosen, or by other means, can beseparated into the pure diastereoisomers or racemates in known manner onthe basis of the physico-chemical differences between the constituents,for example by fractional crystallisation, distillation and/orchromatography.

Correspondingly obtainable mixtures of enantiomers, such as racemates,can be separated into the optical antipodes by known methods, forexample by recrystallisation from an optically active solvent, bychromatography on chiral adsorbents, for example high-pressure liquidchromatography (HPLC) on acetyl cellulose, with the aid of suitablemicro-organisms, by cleavage with specific, immobilised enzymes, or viathe formation of inclusion compounds, for example using chiral crownethers, only one enantiomer being complexed, or by conversion intodiastereoisomeric salts and separation of the resulting mixture ofdiastereoisomers, for example on the basis of their differentsolubilities, by fractional crystallisation, into the diastereoisomersfrom which the desired enantiomer can be freed by the action of suitableagents.

Apart from by separation of corresponding mixtures of isomers, purediastereoisomers and enantiomers can be obtained according to theinvention also by generally known methods of diastereoselectivesynthesis and enantioselective synthesis, respectively, for example bycarrying out the process according to the invention using startingmaterials having correspondingly suitable stereochemistry.

In each case it is advantageous to isolate or synthesise thebiologically more active isomer, e.g. enantiomer or diastereoisomer, ormixture of isomers, e.g. mixture of enantiomers or mixture ofdiastereoisomers, where the individual components have differingbiological activity.

The compounds of formula (I) in free form or in salt form may also beobtained in the form of their hydrates and/or may include othersolvents, for example solvents which may have been used for thecrystallisation of compounds in solid form.

The invention relates to all those embodiments of the process accordingto which a compound obtainable as starting material or intermediate atany stage of the process is used as starting material and some or all ofthe remaining steps are carried out or a starting material is used inthe form of a derivative or salt and/or its racemates or antipodes or,especially, is formed under the reaction conditions.

In the process of the present invention it is preferable to use thosestarting materials and intermediates, each in free form or in salt form,which result in the compounds of formula (I), or salts thereof,described at the beginning as being especially valuable.

The invention relates especially to the preparation processes describedin Examples P1 and P2.

In the area of pest control, the compounds of formula (I) according tothe invention are active ingredients exhibiting valuable preventiveand/or curative activity with a very advantageous biocidal spectrum anda very broad spectrum, even at low rates of concentration, while beingwell tolerated by warm-blooded animals, fish and plants. They are,surprisingly, equally suitable for controlling both plant pests andecto- and endo-parasites in humans and more especially in productivelivestock, domestic animals and pets. They are effective against all orindividual development stages of normally sensitive animal pests, butalso of resistant animal pests, such as insects and members of the orderAcarina, nematodes, cestodes and trematodes, while at the same timeprotecting useful organisms. The insecticidal or acaricidal activity ofthe active ingredients according to the invention may manifest itselfdirectly, i.e. in the mortality of the pests, which occurs immediatelyor only after some time, for example during moulting, or indirectly, forexample in reduced oviposition and/or hatching rate, good activitycorresponding to a mortality of at least 50 to 60%.

The action of the compounds according to the invention and thecompositions comprising them against animal pests can be significantlybroadened and adapted to the given circumstances by the addition ofother insecticides, acaricides or nematicides. Suitable additivesinclude, for example, members of the following classes of activeingredient: organophosphorus compounds, nitrophenols and derivatives,formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbonsand Bacillus thuringiensis preparations.

Examples of especially suitable mixing partners include: azamethiphos;chlorfenvinphos; bupirimate; cypermethrin, cypermethrin high-cis;cyromazine; diafenthiuron; diazinon; dichlorvos; dicrotophos;dicyclanil; fenoxycarb; fluazuron; furathiocarb; isazofos; iodfenphos;kinoprene; lufenuron; methacriphos; methidathion; monocrotophos;phosphamidon; profenofos; diofenolan; a compound obtainable from theBacillus thuringiensis strain GC91 or from NCTC11821; pymetrozine;bromopropylate; methoprene; disulfoton; quinalphos; taufluvalinate;thiocyclam; thiometon; aldicarb; azinphos-methyl; benfuracarb;bifenthrin; buprofezin; carbofuran; dibutylaminothio; cartap;chlorfluazuron; chlorpyrifos; cyfluthrin; alpha-cypermethrin;zeta-cypermethrin; deltamethrin; diflubenzuron; endosulfan;ethiofencarb; fenitrothion; fenazaquin; fenobucarb; fenvalerate;formothion; methiocarb; heptenophos; imidacloprid; isoprocarb;methamidophos; methomyl; mevinphos; parathion; parathionmethyl;phosalone; pirimicarb; propoxur; teflubenzuron; terbufos; triazamate;abamectin; fenobucarb; tebufenozide; fipronil; beta-cyfluthrin;silafluofen; fenpyroximate; pyridaben; primicarb; pyriproxyfen;pyrimidifen; nemathorin; nitenpyram; NI-25; acetamiprid; avermectin B₁(abamectin); a plant extract that is active against insects; apreparation comprising nematodes that are active against insects; apreparation obtainable from Bacillus subtilis; a preparation comprisingfungithat are active against insects; a preparation comprising virusesthat are active against insects; AC 303 630; acephate; acrinathrin;alanycarb; alphamethrin; amitraz; AZ 60541; azinphos A; azinphos M;azocyclotin; bendiocarb; bensultap; beta-cyfluthrin; BPMC; brofenprox;bromophos A; bufencarb; butocarboxin; butyl-pyridaben; cadusafos;carbaryl; carbophenothion; chloethocarb; chlorethoxyfos; chlormephos;cis-resmethrin; clocythrin; clofentezine; cyanophos; cycloprothrin;cyhexatin; demeton M; demeton S; demeton-S-methyl; dichlofenthion;dicliphos; diethion; dimethoate; dimethylvinphos; dioxathion;edifenphos; emamectin; esfenvalerate; ethion; ethofenprox; ethoprophos;etrimphos; fenamiphos; fenbutatin oxide; fenothiocarb; fenpropathrin;fenpyrad; fenthion; fluazinam; flucycloxuron; flucythrinate;flufenoxuron; flufenprox; fonophos; fosthiazate; fubfenprox; HCH;hexaflumuron; hexythiazox; IKI-220; iprobenfos; isofenphos; isoxathion;ivermectin; lambda-cyhalothrin; malathion; mecarbam; mesulfenphos;metaldehyde; metolcarb; milbemectin; moxidectin; naled; NC 184;omethoate; oxamyl; oxydemethon M; oxydeprofos; permethrin; phenthoate;phorate; phosmet; phoxim; pirimiphos M; pirimiphos A; promecarb;propaphos; prothiofos; prothoate; pyrachlophos; pyradaphenthion;pyresmethrin; pyrethrum; RH 5992; salithion; sebufos; sulfotep;sulprofos; tebufenpyrad; tebupirimphos; tefluthrin; temephos; terbam;tetrachlorvinphos; thiacloprid; thiamethoxam; thiafenox; thiodicarb;thiofanox; thionazin; thuringiensin; tralomethrin; triarthene;triazophos; triazuron; trichlorfon; triflumuron; trimethacarb;vamidothion; xylylcarb; YI 5301/5302; zetamethrin; DPX-MP062; RH-2485;D2341 or XMC (3,5-xylyl methylcarbamate).

The said animal pests include, for example, those mentioned in EuropeanPatent Application EP-A-736 252, page 5, line 55, to page 6, line 55.The pests mentioned therein are therefore included by reference in thesubject matter of the present invention.

It is also possible to control pests of the class Nematoda using thecompounds according to the invention. Such pests include, for example,root knot nematodes, cyst-forming nematodes and also stem and leafnematodes;

-   -   especially of Heterodera spp., e.g. Heterodera schachtii,        Heterodora avenae and Heterodora trifolii; Globodera spp., e.g.        Globodera rostochiensis; Meloidogyne spp., e.g. Meloidogyne        incognita and Meloidogyne javanica; Radopholus spp., e.g.        Radopholus similis; Pratylenchus, e.g. Pratylenchus neglectans        and Pratylenchus penetrans; Tylenchulus, e.g. Tylenchulus        semipenetrans; Longidorus, Trichodorus, Xiphinema, Ditylenchus,        Apheenchoides and Anguina; especially Meloidogyne, e.g.        Meloidogyne incognita, and Heterodera, e.g. Heterodera glycines.

An especially important aspect of the present invention is the use ofthe compounds of formula (I) according to the invention in theprotection of plants against parasitic feeding pests.

The compounds according to the invention can be used to control, i.e. toinhibit or destroy, pests of the mentioned type occurring on plants,especially on useful plants and ornamentals in agriculture, inhorticulture and in forestry, or on parts of such plants, such as thefruits, blossoms, leaves, stems, tubers or roots, while in some casesplant parts that grow later are still protected against those pests.

Target crops include especially cereals, such as wheat, barley, rye,oats, rice, maize and sorghum; beet, such as sugar beet and fodder beet;fruit, e.g. pomes, stone fruit and soft fruit, such as apples, pears,plums, peaches, almonds, cherries and berries, e.g. strawberries,raspberries and blackberries; leguminous plants, such as beans, lentils,peas and soybeans; oil plants, such as rape, mustard, poppy, olives,sunflowers, coconut, castor oil, cocoa and groundnuts; cucurbitaceae,such as marrows, cucumbers and melons; fibre plants, such as cotton,flax, hemp and jute; citrus fruits, such as oranges, lemons, grapefruitand mandarins; vegetables, such as spinach, lettuce, asparagus,brassicas, carrots, onions, tomatoes, potatoes and paprika; lauraceae,such as avocado, cinnamon and camphor; and tobacco, nuts, coffee,aubergines, sugar cane, tea, pepper, vines, hops, bananas, naturalrubber plants and ornamentals.

Further areas of use of the compounds according to the invention are theprotection of stored goods and storerooms and the protection of rawmaterials, and also in the hygiene sector, especially the protection ofdomestic animals and productive livestock against pests of the mentionedtype, more especially the protection of domestic animals, especiallycats and dogs, from infestation by fleas, ticks and nematodes.

The invention therefore relates also to pesticidal compositions, such asemulsifiable concentrates, suspension concentrates, directly sprayableor dilutable solutions, spreadable pastes, dilute emulsions, wettablepowders, soluble powders, dispersible powders, wettable powders, dusts,granules and encapsulations in polymer substances, that comprise atleast one of the compounds according to the invention, the choice offormulation being made in accordance with the intended objectives andthe prevailing circumstances.

The active ingredient is used in those compositions in pure form, asolid active ingredient, for example, in a specific particle size, orpreferably together with at least one of the adjuvants customary informulation technology, such as extenders, e.g. solvents or solidcarriers, or surface-active compounds (surfactants). In the area ofparasite control in humans, domestic animals, productive livestock andpets it will be self-evident that only physiologically tolerableadditives are used.

As formulation adjuvants there are used, for example, solid carriers,solvents, stabilisers, “slow release” adjuvants, colourings andoptionally surface-active substances (surfactants). Suitable carriersand adjuvants include all substances customarily used. As adjuvants,such as solvents, solid carriers, surface-active compounds, non-ionicsurfactants, cationic surfactants, anionic surfactants and furtheradjuvants in the compositions used according to the invention, therecome into consideration, for example, those described in EP-A-736 252,page 7, line 51 to page 8, line 39.

The compositions for use in crop protection and in humans, domesticanimals and productive livestock generally comprise from 0.1 to 99%,especially from 0.1 to 95%, of active ingredient and from 1 to 99.9%,especially from 5 to 99.9%, of at least one solid or liquid adjuvant,the composition generally including from 0 to 25%, especially from 0.1to 20%, of surfactants (%=% by weight in each case). Whereas commercialproducts will preferably be formulated as concentrates, the end userwill normally employ dilute formulations having considerably lowerconcentrations of active ingredient.

Preferred crop protection products have especially the followingcompositions (%=percent by weight): Emulsifiable concentrates: activeingredient:   1 to 90%, preferably 5 to 20% surfactant:   1 to 30%,preferably 10 to 20% solvent:   5 to 98%, preferably 70 to 85% Dusts:active ingredient:  0.1 to 10%, preferably 0.1 to 1% solid carrier: 99.9to 90%, preferably 99.9 to 99% Suspension concentrates: activeingredient:   5 to 75%, preferably 10 to 50% water:   94 to 24%,preferably 88 to 30% surfactant:   1 to 40%, preferably 2 to 30%Wettable powders: active ingredient:  0.5 to 90%, preferably 1 to 80%surfactant:  0.5 to 20%, preferably 1 to 15% solid carrier:   5 to 99%,preferably 15 to 98% Granules: active ingredient:  0.5 to 30%,preferably 3 to 15% solid carrier: 99.5 to 70%, preferably 97 to 85%

The compositions according to the invention may also comprise furthersolid or liquid adjuvants, such as stabilisers, e.g. vegetable oils orepoxidised vegetable oils (e.g. epoxidised coconut oil, rapeseed oil orsoybean oil), antifoams, e.g. silicone oil, preservatives, viscosityregulators, binders and/or tackifiers as well as fertilisers or otheractive ingredients for obtaining special effects, e.g. acaricides,bactericides, fungicides, nematicides, molluscicides or selectiveherbicides.

The crop protection products according to the invention are prepared inknown manner, in the absence of adjuvants, e.g. by grinding, sievingand/or compressing a solid active ingredient or mixture of activeingredients, for example to a certain particle size, and in the presenceof at least one adjuvant, for example by intimately mixing and/orgrinding the active ingredient or mixture of active ingredients with theadjuvant(s). The invention relates likewise to those processes for thepreparation of the compositions according to the invention and to theuse of the compounds of formula (I) in the preparation of thosecompositions.

The invention relates also to the methods of application of the cropprotection products, i.e. the methods of controlling pests of thementioned type, such as spraying, atomising, dusting, coating, dressing,scattering or pouring, which are selected in accordance with theintended objectives and the prevailing circumstances, and to the use ofthe compositions for controlling pests of the mentioned type. Typicalrates of concentration are from 0.1 to 1000 ppm, preferably from 0.1 to500 ppm, of active ingredient. The rates of application per hectare aregenerally from 1 to 2000 g of active ingredient per hectare, especiallyfrom 10 to 1000 g/ha, preferably from 20 to 600 g/ha.

A preferred method of application in the area of crop protection isapplication to the foliage of the plants (foliar application), thefrequency and the rate of application being dependent upon the risk ofinfestation by the pest in question. However, the active ingredient canalso penetrate the plants through the roots (systemic action) when thelocus of the plants is impregnated with a liquid formulation or when theactive ingredient is incorporated in solid form into the locus of theplants, for example into the soil, e.g. in granular form (soilapplication). In the case of paddy rice crops, such granules may beapplied in metered amounts to the flooded rice field.

The crop protection products according to the invention are alsosuitable for protecting plant propagation material, e.g. seed, such asfruits, tubers or grains, or plant cuttings, against animal pests. Thepropagation material can be treated with the composition beforeplanting: seed, for example, can be dressed before being sown. Theactive ingredients according to the invention can also be applied tograins (coating), either by impregnating the seeds in a liquidformulation or by coating them with a solid formulation. The compositioncan also be applied to the planting site when the propagation materialis being planted, for example to the seed furrow during sowing. Theinvention relates also to such methods of treating plant propagationmaterial and to the plant propagation material so treated.

The following Examples serve to illustrate the invention. They do notlimit the invention. Temperatures are given in degrees Celsius andmixing ratios of solvents are given in parts by volume.

PREPARATION EXAMPLES

P1: Preparation of the Compound of Formula

P1.1: Preparation of the Compound of Formula

60 g of 3-picoline N-oxide and 60 ml of ethyl iodide are mixed withstirring during which the temperature is maintained below 40° C. Thereaction mixture is left to stand for 16 hours. Then 600 ml of water areadded and the aqueous phase is extracted twice with 300 ml of diethylether. 70 g of potassium cyanide in 180 ml of water are added dropwiseto the aqueous phase, with stirring, over a period of 1 hour at 50° C.Stirring is then carried out for one hour, followed by cooling andextraction twice with 300 ml of diethyl ether. The combined etherealphases are washed with saturated sodium chloride solution, dried oversodium sulfate and concentrated. The crude product is distilled at 20mbar at 100-110° C. 280 ml of methanol are saturated with HCl gas, thedistillate is added and boiling is carried out for 7 hours. Thatsolution is cooled to approximately 5° C., and the product whichprecipitates is removed by filtration and dried, yielding compound (A)having a melting point of 234-237° C.

P1.2: Preparation of the Compound of Formula

3 g of compound (A) are added to 30 ml of concentrated hydrochloric acidand the mixture is stirred for 16 hours at 110° C. The mixture isconcentrated by evaporation and the residue is dried in vacuo, yieldingcompound (B).

P1.3: Preparation of the Compound of Formula

190 ml of methanol are placed in a reaction vessel and HCl gas isintroduced, with ice-cooling, until saturation is reached. Then, at 0°C., 41.6 g of compound (B) are added and the mixture is stirred underreflux for 4 hours. The reaction mixture is concentrated to dryness, andthe residue is dissolved in 190 ml of water, rendered alkaline withsodium hydrogen carbonate and extracted three times with 100 ml ofdiethyl ether each time. The combined ethereal phases are dried oversodium sulfate and then evaporated to dryness, yielding the compound offormula (C).

P1.4: Preparation of the Compound of Formula

25.8 g of compound (C) are introduced into 200 ml of diethyl ether,followed by cooling to 5° C. HCl gas is then introduced until saturationis reached, and the temperature is maintained at 110C. The mixture isfiltered and the residue is washed with a small quantity of diethylether and dried in vacuo. The resulting hydrochloride of compound (C) ishydrogenated in 290 ml of acetic acid and 3 g of platinum oxide for 12hours at 4 bar and at room temperature. After filtration of the reactionmixture, concentration is carried out, and the residue is taken up in150 ml of water, adjusted to pH 11 with potassium carbonate andextracted 4 times with approximately 200 ml of methylene chloride. Themethylene chloride phases are combined, dried over sodium sulfate,filtered and concentrated by evaporation, yielding the desired product(D) in the form of an oil.

P1.5: Preparation of the Compound of Formula

3.2 g of sodium are added to 350 ml of methanol and then 21.5 g ofcompound (D) are added. The mixture is stirred at reflux temperature for48 hours, cooled, acidified with acetic acid and concentrated in vacuo.The residue is stirred with 700 ml of methylene chloride and 1 litre ofsaturated potassium carbonate solution, and the aqueous phase isseparated and extracted once with 200 ml of methylene chloride. Thecombined methylene chloride phases are washed with sodium chloridesolution, dried (sodium sulfate), concentrated, and dried under a highvacuum, yielding compound (E) in the form of a yellow oil.

P1.6: Preparation of the Compound of Formula

5 g of the compound of formula (E) are introduced into 80 ml of dimethylsulfoxide. Then, at room temperature, 5.5 g of benzyl bromide and then15 g of diisopropylethylamine are added dropwise and the mixture isstirred at room temperature for 16 hours. The reaction mixture is pouredonto 200 ml of saturated potassium carbonate solution and washed twicewith 200 ml of ethyl acetate each time. The combined organic phases arewashed twice with water and once with saturated sodium chloride solutionand are dried over sodium sulfate. The solvent is then removed byevaporation. The residue is purified on silica gel using ethylacetate/hexane (1:3) as eluant, yielding the compound of formula (F).

P1.7: Preparation of the Compound of Formula

6.8 g of 4-bromobenzotrifluoride are introduced into 40 ml of diethylether under nitrogen. At 5° C., 19 ml of a 1.6-molar n-butyllithiumsolution in hexane are added. Then, 2.5 g of compound (F) are addeddropwise at 5° C. and stirring is continued for one hour at roomtemperature and for 2 hours at 45° C. The mixture is cooled, 60 ml ofacetic acid (10% in water) are added and the mixture is extracted withethyl acetate. The organic phase is washed with water and potassiumcarbonate solution and dried over sodium sulfate, and the solvent isremoved by evaporation. Compound 2.7 is obtained after purification onsilica gel using ethyl acetate/hexane (1:1) as eluant.

P1.8: Preparation of the Compound of Formula

4 g of compound (2.7) are hydrogenated in 40 ml of methanol and 1.2 g ofpalladium-on-carbon (5% Pd on carbon) at room temperature under normalpressure. The reaction mixture is filtered, concentrated in vacuo anddried under a high vacuum, yielding compound (G) in the form of a resin.

P1.9: Preparation of the Compound of Formulae

To 2.9 g of compound (G) in 17 ml of dimethyl sulfoxide there are addedfirst 1.64 g of the compound of formula

-   -   and then 3.6 g of diisopropylethylamine. The reaction mixture is        stirred for 3 hours at room temperature, poured onto saturated        aqueous potassium carbonate solution and extracted twice with        ethyl acetate, and the ethyl acetate phase is washed with water        and dried over sodium sulfate. The ethyl acetate is removed by        evaporation. Purification of the residue on silica gel using        ethyl acetate/hexane (2:1) as eluant yields the desired product        having a melting point of 66-67° C. (Compound 2.6).

P1.10: Preparation of the Title Compound

1.2 g of compound (2.6) are stirred in 40 ml of methanol and 6.7 g ofhydrogen peroxide (30% in water) for 24 hours at a bath temperature of55° C. The reaction mixture is concentrated, dissolved in ethyl acetate,washed twice with water and once with saturated sodium chloridesolution, dried over sodium sulfate and concentrated. The residue isstirred thoroughly with a small quantity of ethyl acetate, and theproduct which precipitates is removed by filtration and washed withhexane, yielding the title compound having a melting point of 188-190°C. (compound 2.5).

P2: Preparation of the Compound of Formula

P2.1: Preparation of the Compound of Formula

A solution of 34.3 ml of ethylmagnesium chloride in 50 ml oftetrahydrofuran is added dropwise at −70° C. to 7.3 g of indiumtrichloride in 200 ml of tetrahydrofuran and, after stirring for 30minutes, the reaction temperature is allowed to rise slowly to roomtemperature. That solution is added to a solution of 14.9 g of3-bromo-4-pyridine carbaldehyde and 2.8 g of PdCl₂ (PPh₃)₂ in 240 ml oftetrahydrofuran and the reaction mixture is heated under reflux for 20hours. 5 ml of methanol are then added and the mixture is concentratedin vacuo, stirred thoroughly with diethyl ether, filtered off andconcentrated in vacuo once more. The residue is chromatographed onsilica gel using ethyl acetate/hexane (1:1), yielding 3-ethyl-4-pyridinecarbaldehyde (I) in the form of a yellow oil.

P2.2: Preparation of the compound of formula

To a solution of 5.76 ml of 4-bromo-benzotrifluoride in 120 ml oftetrahydrofuran there are added dropwise at −70° C. 26.1 ml ofn-butyllithium (1.6M in hexane) and, after stirring for 10 minutes, 5.12g of compound (I). After 1 hour at −70° C., the reaction temperature isallowed to rise slowly to room temperature. 60 ml of 5% acetic acid areadded dropwise, dilution is carried out with 100 ml of tert-butyl methylether, the aqueous phase is separated and the organic phase is washedwith sodium chloride solution, dried and concentrated in vacuo. Theresidue is chromatographed on silica gel using ethyl acetate/hexane(3:1), yielding compound (K) in the form of a yellow oil.

P2.3: Preparation of the compound of formula

To 2.42 ml of oxalyl chloride in 80 ml of dichloromethane there areadded dropwise at −70° C. 4.28 ml of dimethyl sulfoxide in 60 ml ofdichloromethane and, after stirring for 30 minutes, 6.95 g of compound(K) in 40 ml of dichloromethane. After 1 hour, 17 ml of triethylamine in30 ml of dichloromethane are added dropwise and the reaction temperatureis allow to rise slowly to room temperature. The reaction mixture ispoured onto 100 ml of ice-water, and the organic phase is separated,dried, and concentrated in vacuo. The residue is chromatographed onsilica gel using ethyl acetate/hexane (1:1), yielding compound (L) inthe form of a yellow oil.

P2.4: Preparation of the Compound of Formula

To a solution of 3.45 ml of 4-bromo-benzotrifluoride in 100 ml oftetrahydrofuran there are added dropwise at −70° C. 15.6 ml ofn-butyllithium (1.6M in hexane) and, after stirring for 10 minutes, 5.91g of compound (L). The reaction temperature is then allowed to riseslowly to room temperature. 40 ml of acetic acid (5%) are addeddropwise, dilution is carried out with 100 ml of tert-butyl methylether, the aqueous phase is separated and the organic phase is washedwith aqueous sodium chloride solution, dried, and concentrated in vacuo.Recrystallisation from dichloromethane/hexane yields compound (M) in theform of colour-less crystals, m.p. 202-203° C.

P2.5: Preparation of the compound of formula

2.0 g of compound (M) and 1.18 g of compound (H) from Example P1.9 areheated under reflux in 20 ml of nitromethane for 14 hours. The solventis then distilled oft in vacuo. Compound (N) is obtained in the form ofbeige crystals, m.p. 214-220° C., from dichloromethane/diethyl ether.

P2.6: Preparation of Compound 1.10

0.28 g of sodium borohydride is added in portions to 2.51 g of compound(N) in 25 ml of methanol and stirring is carried out for 20 minutes.After the addition of 1 ml of acetone, concentration is carried out invacuo, ethyl acetate is added and the mixture is washed once with waterand once with sodium chloride solution, dried, and concentrated invacuo. Chromatography on silica gel using ethyl acetate/hexane (1:3)yields compound 1.10 in the form of a foam.

-   -   g) Preparation of the Title Compound

0.92 g of compound (1.10) in 15 ml of methanol are stirred with 3.8 mlof hydrogen peroxide (30% in water) at 50° C. for 24 hours. The solventis distilled off in vacuo, ethyl acetate is added to the residue,followed by washing once with water and once with sodium chloridesolution, drying, and concentration in vacuo. The title compound isobtained in the form of colourless crystals, m.p. 207-211° C. (compound1.11), from dichloromethane/diethyl ether/hexane.

Example P3: The further compounds of Tables 1 and 2 can also be preparedin a manner analogous to that described above. In the Tables, m.p. isthe melting point in ° C.; in the column m.p. other physical propertiesare given as well. Me is methyl, Et is ethyl, prop is n-propyl, i-propis isopropyl, i-but is isobutyl, c-prop is cyclopropyl and2-ethyl-2H-tetrazole-5-yl is the substituent of the formula

TABLE 1 Compounds of formula

No. R₁ R₂ q R₅ R₆ m.p. 1.1 CF₃ CF₃ 1 CH₃

115-120 1.2 CF₃ CF₃ 0 CH₃

resin 1.3 CF₃ CF₃ 0 CH₃ NHCOO-i-prop 69-75 1.4 CF₃ CF₃ 1 CH₃NHCOO-i-prop 105-110 1.5 CF₃ CF₃ 0 CH₃ H resin 1.6 CF₃ CF₃ 0 CH₃ NO₂amorphous 1.7 CF₃ CF₃ 0 CH₃ NH₂ amorphous 1.8 CF₃ CF₃ 0 CH₃ NHCOO—CH₂—amorphous C≡CH 1.9 CF₃ CF₃ 1 CH₃ NHCOO—CH₂— amorphous C≡CH 1.10 CF₃ CF₃0 C₂H₅ NHCOO-i-prop amorphous 1.11 CF₃ CF₃ 1 C₂H₅ NHCOO-i-prop 207-2111.12 CF₃ CF₃ 0 OCH₃ 2-ethyl-2H-tetrazole- 62-65 5-yl 1.13 CF₃ CF₃ 0 OCH₃NHCOO-i-prop 65-69 1.14 OCF₃ OCF₃ 0 CH₃ NHCOO-i-prop 1.15 OCF₃ OCF₃ 1CH₃ NHCOO-i-prop 1.16 OCF₃ OCF₃ 0 CH₃

1.17 OCF₃ OCF₃ 1 CH₃

1.18 Cl Cl 0 CH₃ NHCOO-i-prop 1.19 Cl Cl 1 CH₃ NHCOO-i-prop 1.20 CF₃ CF₃0 F NHCOO-i-prop amorphous

TABLE 2 Compounds of formula

No. R₁ R₂ R₅ R₃/R₅ Q R₆ m.p. 2.1 CF₃ CF₃ CH₃ cis 02-ethyl-2H-tetrazole-5-yl resin 2.2 CF₃ CF₃ CH₃ trans 02-ethyl-2H-tetrazole-5-yl resin 2.3 CF₃ CF₃ CH₃ cis 12-ethyl-2H-tetrazole-5-yl 177-179 2.4 CF₃ CF₃ CH₃ trans 12-ethyl-2H-tetrazole-5-yl 150-155 2.5 CF₃ CF₃ CH₃ cis 1 NHCOO-i-prop188-190 2.6 CF₃ CF₃ CH₃ cis 0 NHCOO-i-prop 66-67 2.7 CF₃ CF₃ CH₃ cis 0 H2.8 CF₃ CF₃ OH mixture 0 NHCOO-i-prop resin cis/trans 2.9 CF₃ CF₃ OHmixture 1 NHCOO-i-prop resin cis/trans 2.10 CF₃ CF₃ OMe mixture 0NHCOO-i-prop cis/trans 2.11 CF₃ CF₃ OMe mixture 1 NHCOO-i-prop cis/trans2.12 CF₃ CF₃ F mixture 0 NHCOO-i-prop cis/trans 2.13 CF₃ CF₃ F mixture 0NHCOO-i-prop cis/trans 2.14 CF₃ CF₃ CH₃ cis 0 2-ethyl-2H-tetrazole-5-ylresin 2.15 CF₃ CF₃ CH₃ cis 1 2-ethyl-2H-tetrazole-5-yl 150-155 2.16 CF₃CF₃ CH₃ cis 0 NHCOO-i-prop 66-67 2.17 CF₃ CF₃ CH₃ cis 1 NHCOO-i-prop188-190 2.18 OCF₃ OCF₃ CH₃ cis 0 2-ethyl-2H-tetrazole-5-yl resin 2.19OCF₃ OCF₃ CH₃ cis 1 2-ethyl-2H-tetrazole-5-yl 138-142 2.20 OCF₃ OCF₃ CH₃cis 0 NHCOO-i-prop 67-70 2.21 OCF₃ OCF₃ CH₃ cis 1 NHCOO-i-prop 188-1912.22 CF₃ CF₃ CH₃ cis 0 NHCOO-Et resin 2.23 CF₃ CF₃ CH₃ cis 1 NHCOO-Et193-196 2.24 F F CH₃ cis 0 NHCOO-i-prop resin 2.25 F F CH₃ cis 02-ethyl-2H-tetrazole-5-yl resin 2.26 Cl Cl CH₃ cis 02-ethyl-2H-tetrazole-5-yl resin 2.27 F F CH₃ cis 12-ethyl-2H-tetrazole-5-yl 150-154 2.28 F F CH₃ cis 1 NHCOO-i-prop167-172 2.29 Cl Cl CH₃ cis 1 2-ethyl-2H-tetrazole-5-yl 154-158 2.30 ClCl CH₃ cis 0 NHCOO-i-prop Resin 2.31 Cl Cl CH₃ cis 1 NHCOO-i-prop174-182 2.32 CF₃ CF₃ CH₃ cis 0

Resin 2.33 CF₃ CF₃ CH₃ cis 1

148-151 2.34 CF₃ CF₃ CH₃ cis 0 H Resin 2.35 CF₃ CF₃ CH₃ cis 0 NO₂ Resin2.36 CF₃ CF₃ CH₃ cis 0 NH₂ Resin 2.37 CF₃ CF₃ CH₃ cis 0—NHCO-2-Cl-phenyl 82-87 2.38 CF₃ CF₃ CH₃ cis 0

Resin 2.39 CF₃ CF₃ CH₃ cis 1

185-187 2.40 CF₃ CF₃ CH₃ cis 1 —NHCO-2-Cl-phenyl 170-173 2.41 CF₃ CF₃CH₃ cis 0 —NHCO—NH—Et 140-142 2.42 CF₃ CF₃ CH₃ cis 1 —NHCO—NH—Et 187-1892.43 CF₃ CF₃ Et cis 0 2-ethyl-2H-tetrazole-5-yl Resin 2.44 CF₃ CF₃ Etcis 1 2-ethyl-2H-tetrazole-t-yl 145-147 2.45 CF₃ CF₃ Et cis 0NHCOO-i-prop Resin 2.46 CF₃ CF₃ Et cis 1 NHCOO-i-prop 167-169 2.47 CF₃CF₃ CH₃ cis 0 NHCOO-Me resin 2.48 CF₃ CF₃ CH₃ cis 1 NHCOO-Me 155-1572.49 OCF₃ OCF₃ CH₃ cis 0 NHCOO-Me 2.50 OCF₃ OCF₃ CH₃ cis 1 NHCOO-Me 2.51CF₃ OCF₃ CH₃ cis 0 NHCOO-i-prop 2.52 CF₃ OCF₃ CH₃ cis 1 NHCOO-i-prop2.53 CF₃ OCF₃ CH₃ cis 0 2-ethyl-2H-tetrazole-5-yl 2.54 CF₃ OCF₃ CH₃ cis1 2-ethyl-2H-tetrazole-5-yl 2.55 CF₃ CF₃ Prop cis 0 NHCOO-i-prop 2.56CF₃ CF₃ Prop cis 1 NHCOO-i-prop 2.57 CF₃ CF₃ Prop cis 02-ethyl-2H-tetrazole-5-yl 2.58 CF₃ CF₃ Prop cis 12-ethyl-2H-tetrazole-5-yl 2.59 CF₃ CF₃ CH₃ trans 02-ethyl-2H-tetrazole-5-yl Resin 2.60 CF₃ CF₃ CH₃ trans 12-ethyl-2H-tetrazole-5-yl 177-179 2.61 OCF₃ OCF₃ CH₃ trans 0NHCOO-i-prop 79-81 2.62 OCF₃ OCF₃ CH₃ trans 1 NHCOO-i-prop 148-152 2.63OCF₃ OCF₃ CH₃ trans 0 2-ethyl-2H-tetrazole-5-yl 68-70 2.64 OCF₃ OCF₃ CH₃trans 1 2-ethyl-2H-tetrazole-5-yl 138-142

FORMULATION EXAMPLES %=Percent by Weight

Example F1: Emulsifiable concentrates a) b) c) active ingredient 25% 40%50% calcium dodecylbenzenesulfonate  5%  8%  6% castor oil polyethyleneglycol ether  5% — — (36 mol EO) tributylphenol polyethylene glycolether — 12%  4% (30 mol EO) cyclohexanone — 15% 20% xylene mixture 65%25% 20%

Mixing finely ground active ingredient and additives gives anemulsifiable concentrate which yields emulsions of the desiredconcentration on dilution with water. Example F2: Solutions a) b) c) d)active ingredient 80% 10%  5% 95% ethylene glycol monomethyl ether 20% —— — polyethylene glycol (MW 400) — 70% — — N-methylpyrrolid-2-one — 20%— — epoxidised coconut oil — —  1%  5% benzine (boiling range: 160-190°)— — 94% —

Mixing finely ground active ingredient and additives gives a solutionsuitable for use in the form of microdrops. Example F3: Granules a) b)c) d) active ingredient  5% 10%  8% 21% kaolin 94% — 79% 54% highlydispersed silicic acid  1% — 13%  7% attapulgite — 90% — 18%

The active ingredient is dissolved in dichloromethane, the solution issprayed onto the carrier mixture and the solvent is evaporated off invacuo.

BIOLOGICAL EXAMPLES Example B1 Action against Heliothis VirescensCaterpillars

Young soybean plants are sprayed with an aqueous emulsion spray mixturecomprising 400 ppm of test compound. After the spray-coating has dried,the soybean plants are populated with 10 caterpillars of Heliothisvirescens in the first stage and placed in a plastics container.Evaluation is made 6 days later. The percentage reduction in populationand the percentage reduction in feeding damage (% activity) aredetermined by comparing the number of dead caterpillars and the feedingdamage on the treated plants with that on untreated plants.

The compounds of the Tables exhibit good activity against Heliothisvirescens in this test. In particular, compounds 1.9, 2.2, 2.4, 2.5 and2.6 are more than 80% effective.

Example B2 Action Against Plutella Xylostella Caterpillars

Young cabbage plants are sprayed with an aqueous emulsion spray mixturecomprising 400 ppm of test compound. After the spray-coating has dried,the cabbage plants are populated with 10 caterpillars of Plutellaxylostella in the third stage and placed in a plastics container.Evaluation is made 3 days later. The percentage reduction in populationand the percentage reduction in feeding damage (% activity) aredetermined by comparing the number of dead caterpillars and the feedingdamage on the treated plants with that on the untreated plants.

The compounds of the Tables exhibit good activity against Plutellaxylostella in this test. In particular, compounds 1.9, 2.2, 2.4, 2.5 and2.6 are more than 80% effective.

Example B3 Action Against Diabrotica Balteata Caterpillars

Maize seedlings are sprayed with an aqueous emulsion spray mixturecomprising 400 ppm of the test compound. After the spray-coating hasdried, the maize seedlings are populated with 10 Diabrotica balteatalarvae in the second stage and placed in a plastics container.Evaluation is made 6 days later. The percentage reduction in population(% activity) is determined by comparing the number of dead larvae on thetreated plants with that on untreated plants.

The compounds of the Tables exhibit good activity against Diabroticabalteata in this test. In particular, compounds 1.9, 2.2, 2.4, 2.5 and2.6 are more than 80% effective.

Example B4 Action Against Spodoptera Littoralis

Young soybean plants are sprayed with an aqueous emulsion spray mixturecomprising 400 ppm of test compound. After the spray-coating has dried,the soybean plants are populated with 10 caterpillars of Spodopteralittoralis in the third stage and placed in a plastics container.Evaluation is made 3 days later. The percentage reduction in populationand the percentage reduction in feeding damage (% activity) aredetermined by comparing the number of dead caterpillars and the feedingdamage on the treated plants with that on untreated plants.

The compounds of the Tables exhibit good activity against Spodopteralittoralis in this test. In particular, compounds 1.9, 2.2, 2.4, 2.5 and2.6 are more than 80% effective.

1. A compound of formula

wherein R₁ and R₂ are each independently of the other hydrogen, halogen,C₁-C₆alkyl, C₃-C₆-cycloalkyl, halo-C₁-C₆alkyl, halo-C₃-C₆cycloalkyl,C₂-C₄alkenyl, C₂-C₄alkynyl, halo-C₂-C₄alkenyl, halo-C₂-C₄alkynyl,C₁-C₆alkoxy, halo-C₁-C₆alkoxy, C₂-C₆alkenyloxy, C₂-C₆alkynyloxy,halo-C₂-C₆alkenyloxy, halo-C₂-C₆alkynyloxy, —SF₅, —C(═O)N(R₇)₂,—O—C(═O)N(R₇)₂, —CN, —NO₂, —S(═O)₂N(R₇)₂, —S(═O)P—C₁-C₆alkyl,—S(═O)_(p)-halo-C₁-C₆alkyl, —O—S(═O)_(p)—C₁-C₆alkyl,—O—S(═O)_(p)-halo-C₁-C₆alkyl, phenyl, benzyl, phenoxy or benzyloxy,wherein each of the phenyl, benzyl, phenoxy or benzyloxy radicals isunsubstituted or is substituted in the aromatic ring by from one to fivesubstituents selected independently of one another from the groupconsisting of halogen, cyano, NO₂, C₁-C₆alkyl, halo-C₁-C₆alkyl,C₁-C₆alkoxy and halo-C₁-C₆alkoxy; R₃ and R₄ are hydrogen or togetherform a bond; R₅ is C₁-C₆alkyl, halo-C₁-C₆alkyl, C₃-C₆cycloalkyl,C₂-C₄alkenyl, C₂-C₄alkynyl, C₁-C₆-alkoxy, C₁-C₆alkoxyalkyl,halo-C₁-C₆alkoxy, C₂-C₆alkenyloxy, C₂-C₆alkynyloxy, C₁-C₆alkylthio,C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, halogen or hydroxy; R₅₅ ishydrogen, C₁-C₆alkyl, halo-C₁-C₆alkyl, C₃-C₆cycloalkyl, C₂-C₄alkenyl,C₂-C₄alkynyl, C₁-C₆alkoxy, C₁-C₆alkoxyalkyl, halo-C₁-C₆alkoxy,C₂-C₆alkenyloxy or C₂-C₆alkynyloxy; R₆ is hydrogen, halogen, CN, NO₂,C₁-C₆alkyl, halo-C₁-C₆alkyl, C₃-C₆cycloalkyl, halo-C₃-C₆cycloalkyl,C₃-C₆cycloalkoxy, C₁-C₆alkoxy, halo-C₁-C₆alkoxy, C₂-C₄alkenyl,C₂-C₄-alkynyl, halo-C₂-C₄alkenyl, halo-C₂-C₄alkynyl, C₂-C₆alkenyloxy,C₂-C₆alkynyloxy, halo-C₂-C₆alkenyloxy, halo-C₂-C₆alkynyloxy,—C(═O)-C₁-C₆alkyl, —C(═O)-halo-C₁-C₆alkyl, —C(═O)—OC₁-C₆alkyl,—C(═O)—O-halo-C₁-C₆alkyl, —N(R₇)₂, —C(═O)N(R₇)₂, —O—C(═O)N(R₇)₂,—S(═O)₂N(R₇)₂, —S(═O)_(p)—C₁-C₆alkyl, —S(═O)_(p)-halo-C₁-C₆alkyl,—O—S(═O)_(p)—C₁-C₆alkyl, —O—S(═O)_(p)-halo-C₁-C₆alkyl,—NR₁₂—C(═Y)—Z—R₁₃, —C(R₉)═N—W—R₁₀, benzyl, phenoxy, benzyloxy; orphenyl, benzyl, phenoxy, benzyloxy, heterocyclyl or heterocyclyloxy eachof which is substituted by from one to five substituents selectedindependently of one another from the group consisting of halogen,cyano, NO₂, C₁-C₆alkyl, C₃-C₈cycloalkyl, C₃-C₈cycloalkyl-C₁-C₆alkyl,halo-C₁-C₆alkyl, C₁-C₆alkoxy, C₃-C₈cycloalkoxy,C₃-C₈cycloalkoxy-C₁-C₆alkyl, C₃-C₈cycloalkyl-C₁-C₆alkoxy,halo-C₁-C₆alkoxy, C₂-C₄alkenyl, C₂-C₄alkynyl, halo-C₂-C₄alkenyl,halo-C₂-C₄alkynyl, C₂-C₆alkenyloxy, C₂-C₆alkynyloxy,halo-C₂-C₆alkenyloxy, halo-C₂-C₆alkynyloxy, —N(R₈)₂, phenyl, benzyl,phenoxy, benzyloxy, heterocyclyl and heterocyclyloxy; the two R₇radicals are each independently of the other hydrogen, C₁-C₁₋₂alkyl,halo-C₁-C₁₂alkyl, C₂-C₁₂alkenyl, halo-C₂-C₁₂alkenyl, C₂-C₁₂alkynyl,halo-C₂-C₁₂alkynyl, —C(═O)—R₁₀, —C(═S)—R₁₀, —C(═O)—O—R₁₀, —C(═S)—O—R₁₀,—C(═O)—NR₁OR₁₁, —C(═S)—NR₁₀R₁₁, —S(═O)_(p)—R₁₀, C₃-C₈cycloalkyl, aryl,aryl-C₁-C₆alkyl, heterocyclyl, heterocyclyl-C₁-C₆alkyl; orC₃-C₈cycloalkyl, aryl, aryl-C₁-C₆alkyl, heterocyclyl orheterocyclyl-C₁-C₆alkyl which, depending upon the possibilities ofsubstitution, are each substituted in the ring by from one to fivesubstituents selected independently of one another from halogen,hydroxy, cyano, nitro, C₁-C₆alkyl, halo-C₁-C₆alkyl, C₁-C₆alkoxy andhalo-C₁-C₆alkoxy; or together, with the nitrogen atom to which they arebonded, form a heterocyclic ring that is unsubstituted or substituted;R₈ is hydrogen, C₁-C₆alkyl or benzyl; R₉ is halogen, C₁-C₆alkyl,C₃-C₈cycloalkyl, C₃-C₈cycloalkyl-C₁-C₆alkyl, halo-C₁-C₆alkyl,C₁-C₆alkoxy, C₃-C₈cycloalkoxy, C₃-C₈cycloalkoxy-C₁-C₆alkyl,halo-C₁-C₆alkoxy, —NH(C₁-C₆alkyl) or —N(C₁-C₆alkyl)₂; R₁₀ and R₁₁ areeach independently of the other hydrogen, C₁-C₆alkyl, C₃-C₈cycloalkyl,C₃-C₈cycloalkyl-C₁-C₆alkyl, halo-C₁-C₆alkyl, C₂-C₄alkenyl, C₂-C₄alkynyl,halo-C₂-C₄alkenyl, halo-C₂-C₄alkynyl or —C(═O)-C₁-C₆alkyl; R₁₂ ishydrogen, C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl, C₃-C₈cycloalkyl,halo-C₁-C₆alkyl, C₂-C₆alkenyl or C₂-C₆alkynyl; R₁₃ is hydrogen,C₁-C₆alkyl, halo-C₁-C₆alkyl, C₁-C₆alkoxy-C₁-C₆alkyl, C₃-C₈cycloalkyl,halo-C₁-C₆alkyl, halo-C₃-C₈cycloalkyl, C₂-C₆alkenyl, C₂-C₆alkynyl,halo-C₂-C₆alkenyl, halo-C₂-C₆alkynyl, aryl, aryl-C₁-C₆alkyl orheterocyclyl, or aryl, aryl-C₁-C₆alkyl or heterocyclyl each of which issubstituted by from one to three substituents selected from the groupconsisting of halogen, cyano, NO₂, C₁-C₆alkyl, C₃-C₈cycloalkyl,halo-C₁-C₆alkyl, C₁-C₆alkoxy, halo-C₁-C₆alkoxy, C₂-C₄alkenyl,C₂-C₄alkynyl, halo-C₂-C₄alkenyl, halo-C₂-C₄alkynyl, C₂-C₆alkenyloxy andC₂-C₆alkynyloxy; m is 1, 2, 3, 4 or 5; n is 1, 2, 3, 4 or 5; o is 1, 2or 3; p is 0, 1 or 2; q is 0 or 1; s is 1, 2, 3, 4 or 5; Y is O or S; Zis a bond, O, S or NR₁₄; R₁₄ is hydrogen, C₁-C₆alkyl,C₁-C₆alkoxy-C₁-C₆alkyl, C₃-C₈cycloalkyl, halo-C₁-C₆alkyl, C₂-C₆alkenylor C₂-C₆alkynyl; W is O or NH or N-C₁-C₆alkyl; or, where applicable, anE/Z isomer, a mixture of E/Z isomers and/or a tautomer, in each case infree form or in salt form.
 2. A compound according to claim 1 of formula(I) wherein R₃ and R₅ are cis to each other.
 3. A compound according toclaim 1 of formula (I) wherein R₃ and R₄ are hydrogen.
 4. A compoundaccording to claim 3 of formula (1) wherein R₅ is C₁-C₆alkyl orhalo-C₁-C₆alkyl.
 5. A pesticidal composition comprising as activeingredient at least one compound of formula (I) as described in claim 1,in free form or in agrochemically acceptable form, and at least oneadjuvant.
 6. A process for the preparation of a composition as describedin claim 5, which comprises intimately mixing the active ingredient withthe adjuvant(s).
 7. A method of controlling pests, which comprisesapplying as active ingredient a compound according to claim 1 of formula(I), in free form or, where applicable, in agrochemically acceptablesalt form, to the pests or to the locus thereof.
 8. Canceled.